Reactive dyes containing a halobenzene nucleus

ABSTRACT

This application relates to reactive dyes having at least one halobenzene nucleus linked to a chromophoric group via an amino linkage and additionally containing a second reactive group.

This invention relates to reactive dyes containing a halobenzene nucleusand, in particular, reactive dyes of this type containing two or morereactive components.

Dyes are known which contain a halobenzene nucleus linked via an azogroup to another aromatic nucleus such that the halobenzene nucleusforms part of the chromophoric chain (see for example GB-A-882001). Dyesof this type which contain two such halobenzene nuclei are disclosed inCA64,14316d (1966), which is an English language abstract of an articleby Matsui et al, Yuki Gosei Kagaku Kyokai Shi (1966), 24(2), 132-136.

Dyes are also known in which the halobenzene nucleus is attached to achromophoric group by a sulphonamide or amide linkage; see, for example,GB-A-978162 and CA59,12949g (1963), which is an English languageabstract of an article by Matsui et al in Yuki Gosei Kagaku Kyokai Shi(1962), 20,1100-1112. Again dyes of this type may contain two suchhalobenzene nuclei; see GB-A-978162.

In other known dyes the halobenzene nucleus is linked to a chromophoricgroup by an amine linkage; see U.S. Pat. No. 3,301,847 and CA61,16193f(1964) which is an English language abstract of an article by Matsui etal in Kogyo Kagaku Zasshi, (1964), 67(1),94-97. However, such dyescontain only one reactive group.

We have now found surprisingly that dyes having at least one halobenzenenucleus linked to a chromophoric group via an amino linkage andadditionally containing a second reactive group have particularly highbuild up, especially in warm dyeing applications.

According to the invention there is provided a dye containing

at least one chromophore D;

at least a first, halobenzene, reactive group Z¹, of the formula (I)

in which:

n is 1 or 2

X, or each X independently, is an electron withdrawing group; and

Y is a halogen atom;

at least a second reactive group Z² selected from

(1) a group of the formula (I), given and defined above, but selectedindependently thereof;

(2) a group of the formula (II)

wherein

m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2, p is 0;

Y¹, or each Y¹ independently, is a halogen atom or an optionallysubstituted pyridinium group; and

T is C₁₋₄alkoxy, C₁₋₄thioalkoxy or N(R¹)(R²), in which each of R¹ and R²independently is hydrogen, optionally substituted C₁₋₄alkyl oroptionally substituted aryl;

(3) a group of the formula (III)

wherein:

x is 1, 2 or 3; y is zero, 1 or 2; and

x+y≦3;

Y², or each Y² independently, is a halogen atom or an optionallysubstituted pyridinium group; and

U or each U independently, is C₁₋₄alkyl or C₁₋₄alkylsulphonyl;

(4) a group of the formula (IV)

—SO₂CH₂CH₂X¹  (IV)

wherein X¹ is an eliminatable group;

(5) a group of the formula (V)

—SO₂(CH₂)_(z)CH═CH₂  (V)

wherein z is zero or 1; and

(6) a group of formula (VI)

—W—C(R¹⁰)═CH₂  (VI)

wherein:

R¹⁰ is hydrogen, C₁₋₄alkyl or halogen; and

W is —OC(═O)— or —N(R¹¹)C(═O)— in which R¹¹ is hydrogen or C₁₋₄ alkyl;

at least a first linking group L¹, linking the said first, halobenzene,reactive group Z¹ to one of components (i) the or a chromophore D and(ii) the second reactive group Z², which said first linking group L¹presents an amino nitrogen to the reactive group Z¹ and to the component(i) or (ii) or, when component (i) contains a heterocyclic nitrogenatom, is linked directly to the nitrogen atom and which said firstlinking group L¹ optionally includes a hydrocarbon bridging group, whichhydrocarbon bridging group B has at least two carbon atoms, isoptionally substituted, optionally includes at least one hetero atom andis optionally a chromophore; and

when Z² is selected from the said groups (I)-(III), at least a secondlinking group L² linking the second reactive group Z² to one of (i) theor a chromophore D and (ii) the said first reactive group Z¹, which saidlinking group L² is selected from

(1) a linking group L¹, but selected independently thereof; or

(2) an amide linkage; and

(3) a sulphonamide linkage; and

optionally at least one aromatic group Ar which, when Z² is selectedfrom the said groups (IV)-(VI), may carry the said reactive group Z².

Preferably, the linking group L¹ has the formula (VII)¹

N(R)  (VII)¹

wherein R is hydrogen or optionally substituted C₁₋₄alkyl, such that thesame amino group presents itself to each of the reactive group Z¹ andthe component (i) or (ii), as defined above; or

is a piperazinoalkylamino group of the formula (VII)²

wherein each R, independently, is as defined above, such that respectiveamino nitrogens, one of the piperazine group and the other of thealkylamino group, present themselves respectively, to the reactive groupZ¹ and to the component (i) or (ii), as defined above; or

has the formula (VII)³

—N(R)BN(R)—  (VII)³

wherein B is a hydrocarbon bridging group as defined above, each R,independently, is as defined above and B is optionally linkedadditionally to at least one additional group —N(R).

The hydrocarbon bridging group B may be a straight or branched,optionally substituted, C₂₋₆alkylene group optionally interrupted by atleast one hetero atom, for example, O, S or N. Optional substituents areOH alkoxy, carboxy, carboxylic ester or carboxamide. Alternatively thebonding group B may be an optionally substituted arylene especiallyphenylene group. Optional substituents are SO₃H and salts thereof,C₁₋₄alkyl, C₁₋₄alkoxy and chloro. The bridging group B is especiallypreferably an optionally substituted aryl group.

An especially preferred dye embodying the invention has the formula(VIII)

Z¹—L¹—D—(L²)_(a)—Z²  (VIII)

wherein:

D is a chromophore;

each of L¹ and L² is an amine or piperazine linkage of the formula

—N(R)— (VII)¹;

wherein:

R, or each R independently, is hydrogen or C₁₋₄ alkyl;

B is a hydrocarbon bridging group which has at least two carbon atoms,is optionally substituted, optionally includes at least one hetero atomand is optionally a chromophore;

a is zero or 1; and

b is from 2 to 6 inclusive;

Z¹ is a group

in which:

n is 1 or 2;

X, or each X independently, is an electron withdrawing group; and

Y is a halogen atom; and

when a is 1, Z² is:

a group of the formula (I), given and defined above but selectedindependently thereof; or

a group of the formula (II)

wherein:

m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2, p is 0;

Y¹, or each Y¹ independently, is a halogen atom or an optionallysubstituted pyridinium group; and

T is C₁₋₄ alkoxy, thioalkoxy or N(R¹)(R²) in which R¹ is hydrogen,optionally substituted C₁₋₄ alkyl or optionally substituted aryl and

R² is hydrogen or optionally substituted C₁₋₄ alkyl; or

a group of the formula (III)

wherein:

x is 1, 2 or 3; y is zero, 1 or 2; and x+y≦3;

Y², or each Y² independently, is a halogen atom; and

U, or each U independently, is C₁₋₄ alkyl or C₁₋₄ alkylsulphonyl; and

when a is zero, Z² is:

—SO₂CH₂CH₂X¹  (IV)

in which X¹ is an eliminatable group; or

—SO₂(CH₂)_(z)CH—CH₂  (V)

wherein

z is zero or 1; or

a group of formula (VI)

—W—C(R¹⁰)═CH₂  (VI)

wherein:

R¹⁰ is hydrogen, C₁₋₄alkyl or halogen; and

W is —OC(═O)— or —N(R¹¹)C(═O)— in which R¹¹ is hydrogen or C₁₋₄ alkyl.

In the halobenzene nucleus of the formula (I), X or each Xindependently, may be selected from nitro, cyano, alkylsulphonyl,dialkylaminosulphonyl and sulphonic acid groups and salts thereof.Preferably, X or each X independently, is selected from nitro and cyano.

The halogen atom in the halobenzene nucleus of formula (I) is preferablyfluorine or chlorine.

The group R in the linking group L¹ of formulae (1)-(3) may be any ofhydrogen, methyl, ethyl, n- or i-propyl or n-, s- or t-butyl, but ispreferably hydrogen.

In the dye of formula (VII), each of Z¹ and Z², independently, ispreferably a group of the above mentioned formula (I). Moreover, it iseven more preferred that each of Z¹ and Z² is the same group as theother.

However, alternatively, Z¹ may be a halobenzene nucleus of the formula(I), A may be zero and Z² a group of the formula

—SO₂CH₂CH₂X¹  (IV)

in which X¹ is an eliminatable group such as OSO₃H, OPO₃H₂ and salts ofany of these, and Cl, a preferred group (IV) being

—SO₂CH₂CH₂OSO₃H

(or a salt thereof)

or

—SO₂(CH₂)_(z)CH═CH₂  (V)

wherein z is zero or 1.

In an other alternative range of dyes, Z¹ is a halobenzene nucleus ofthe formula (I) above and Z² is a halotriazine nucleus of the formula(II)

wherein m is 1 or 2, p is 0 or 1,

when m is 1, p is 1 and

when m is 2, p is 0;

Y¹, or each Y¹ independently, is a halogen atom or an optionallysubstituted pyridinium group; and

T is C₁₋₄ alkoxy, C₁₋₄thioalkoxy or N(R¹)(R²) in which R¹ is hydrogen,optionally substituted C₁₋₄alkyl or optionally substituted aryl; and

R² is hydrogen or optionally substituted C₁₋₄alkyl.

In the above formula (II), Y¹ is preferably fluorine, chlorine oroptionally substituted pyridinium which may be derived from, forexample, nicotinic or isonicotinic acid or their carboxamides.

Each of R¹ and R² is preferably hydrogen, but at least one of R¹ and R²may be a C₁₋₄ alkyl group and indeed R¹ may additionally be anoptionally substituted aryl, preferably phenyl, group.

When such a C₁₋₄ alkyl or aryl group is substituted, a preferredsubstituent is hydroxyl, amino, halo, carboxy or sulpho.

In yet another alternative dye in accordance with the invention, Z¹ is ahalobenzene nucleus of the formula (I) and Z² is a halopyrimidinenucleus of the formula

wherein

x is 1, 2 or 3; y is 0, 1 or 2; and x+y≦3;

Y², or each Y² independently, is halogen atom; and

U, or each U independently, is C₁₋₄alkyl or C₁₋₄alkylsulphonyl.

In the above formula (III) Y² is preferably fluorine or chlorine.

A preferred range of dyes embodying the invention has the formula (XXX)

Z¹—L¹—D[L³]_(q)—[Z³—L⁴ _(r)[J¹]_(s)[L²]_(a)Z²[L⁵—J²]_(t)  (XXX)

wherein:

Z³ is a third reactive group selected from the groups of the formulae(I)-(III), given and defined above;

each of J¹ and J², independently, is an optionally substituted arylgroup or a chromophore;

L³ is a linking group linking Z³ and D;

L⁴ is a linking group linking Z³ and J¹;

L⁵ is a linking group linking Z³ and J²;

each of q, r, s and t independently, is zero or 1;

each of Z¹, Z², L¹, L² and a is as defined above; and

when at least one of a and t is 1, Z² is selected from the groups of theformulae (I)-(III), given and defined above.

In one such range of dyes, q is 1, r is 1, s is 1, each of a and t iszero and Z² is selected from the groups of the formulae (IV)-(VI), givenand defined above.

In another such range, q is 1, r is 1, s is zero, a is zero and t is 1.

In a dye of the formula (XXX), each of L³ and L⁴, independently, ispreferably selected from one of the groups of the formulae (VII)¹,(VII)² and (VII)³, given and defined above;

each of L³ and L⁴ is preferably a group of the formulae (VII)¹, givenand defined above.

In one preferred range of dyes of the formula (XXX), q is 1, r is zero,s is 1, a is zero and t is zero and in such a range L³ is preferably agroup of the formula (VII)³

—N(R)BN(R)—  (VII)³

wherein B is a triazine group substituted by a non reactive group.

In a dye of the formula (XXX), the chromophore D is preferably an azochromophore derived from 1-hydroxy-8-aminonaphthalene substituted by atleast one sulphonic acid group.

Yet another range of dyes embodying the invention has the formula

Z¹—L¹—D¹[L³—Z³(L⁴—Z⁴)_(l)L⁵—D²]_(k)[L²]_(a)Z²

wherein:

D¹ is a first chromophore;

D² is a second chromophore;

Z³, when present, is a third reactive group selected from the groups ofthe formulae (I)-(III), given and defined in claim 1;

Z⁴, when present, is a fourth reactive group selected from the groups ofthe formulae (I)-(III), given and defined in claim 1;

L³ is a linking group linking Z³ to D¹;

L⁴ is a linking group linking Z³ to Z⁴;

L⁵ is a linking group linking D² to one of Z³ and Z⁴;

each of k and l, independently, is zero or 1; and

each of Z¹, Z², L¹, L² and a is as defined in claim 1.

In one range of such dye of formula (XXXI), a is 1, Z² is a group of theformula (I), given and defined above, k is zero and D¹ is a tetrakisazochromophore containing two residues of H-acid linked together by a groupforming part of the chromophore.

In another such range, a is 1, each of Z¹ and Z² is a group of theformula (I), given and defined above, each of k and l is 1;

each of D¹ and D² is a disazo chromophore containing a respectiveresidue of H-acid,

each of Z¹ and Z⁴ is a group of the formula (II), given and definedabove, and

L⁴ is a linking group of the formula (VII)²

or (VII)³, given and defined above.

In still further such ranges

(i) a is 1, Z² is a group of the formula (I), given and defined above, kis 1 and l is 1; or

(ii) a is 1, Z³ is a group of the formula (I), given and defined above,k is 1 and l is zero.

Yet another preferred range of dyes embodying the invention has theformula (XXXII)

Z¹—L¹—Z³—L³—D—Z²  (XXXII)

wherein:

Z³ is a third reactive group selected from the groups (I)-(III), givenand defined above; and

L³ is a third linking group selected from the groups (VII)¹, (VII)² and(VII)³, given and defined above;

Z² is a second reactive group selected from the groups (IV)-(VI), givenand defined above; and

each of Z¹ and L¹ is as defined above.

In such dyes of the formula (XXXII), L¹ is preferably a linking group ofthe formula (VII)² or (VII)³, given and defined above and Z³ ispreferably a group of the formula (II), given and defined above.

Another range of dyes embodying the invention has the formula (XXXIII)

Other ranges of dyes embodying the invention are of the respectiveformulae

D²—L²—Z²—L³—D¹—L¹—Z¹  (XXXIV)

wherein:

each of D¹ and D², independently, is a chromophore;

L³ is a linking group selected from groups of the formula (I)-(III),given and defined above; and

each of Z¹, Z², L¹ and L² is as defined above; and

wherein:

each of D¹ and D², independently, is a chromophore;

L³ is a linking group selected from the groups of the formulae(I)-(III), given and defined above; and

each of Z¹, Z², L¹ and L² is as defined above; and

wherein:

one of Z³ and Z⁴ is a reactive group Z²;

D—L²—Z²—L¹—Z¹  (XXXIII)

wherein:

Z² is selected from groups of the formulae I-(III), given and definedabove; and

each of D, Z¹, L¹ and L² is as defined above.

In such dyes of the formula (XXXIII), Z² is preferably a group of theformula (II), given and defined above and L² is preferably a linkinggroup selected from the groups (VII)¹, (VII)² and (VII)³, given anddefined above, more preferably a group of the formula (VII)² or (VII)³,given and defined above; and L¹ is a group of the formula (VII)³, givenand defined above, in which B is an optionally substituted aryl group,or is alternatively a chromophoric bridging group.

In the range of dyes of formulae (XXXII), a preferred chromophore D is adisazo dye containing a residue derived from H-acid and having azogroups at the 2- and 7-positions.

Another preferred chromophore D is a group of the formula

each of Z³ and Z⁴, independently, is a reactive group selected from theformulae (IV)-(VI), given and defined above;

each of t and u, independently, is zero or 1 and at least one of t and uis 1;

D is a chromophore;

Ar is an optionally substituted aryl group;

L¹ is a group of the formula

wherein each R, independently, is as defined in claim; and

Z¹ is as defined above.

In such dyes of formulae (XXXVI), D is preferably a disazo dyecontaining a residue derived from H-acid.

In a dye embodying the invention, the or a chromophore D may contain aheterocyclic nitrogen atom, in which case the linking group may have theformula

wherein each of B, R and b is as defined above and the bond {circlearound (1)} is linked to the heterocyclic nitrogen atom of thechromophore.

Such dyes, may have the formula

Z¹—L¹—D^(N)L²_(a)Z²L⁵—Ar]_(t)

wherein:

D^(N) is a chromophore containing a heterocyclic group including anitrogen atom;

L¹ is a group of the formula (VII)⁴ or (VII)⁵, given and defined above,directly attached via the bond {circle around (1)}, to the nitrogen atomof the said chromophore D^(N);

Ar is an optionally substituted aryl group;

and each of Z¹, Z², L², L⁵, a and t is as defined above.

A typical chromophore D containing a heterocyclic nitrogen atom has theformula

In the above formulae, wherever L¹-L⁵, J¹, J² or B is or has anoptionally substituted phenyl group, optional substituents are SO₃H or asalt thereof, C₁₋₄alkyl, especially methyl and chloro, especially SO₃H.

Again, in all of the above formulae, where the groups Z² is any of thegroups of the formulae (I)-(III), it is most preferably of the formula(II).

Likewise in all such formulae, where Z² is any of the groups (IV)-(VI),it is most preferably of the formula (IV) or (V), wherein Z is zero.

In a dye according to the invention, in general, the or eachchromophoric group independently preferably comprises an azo (which maybe a monoazo, polyazo or metal complex azo), anthraquinone, hydrazone,phthalocyanine, triphenodioxazine or formazan group. Examples ofchromophoric groups which may be present are those given as types(a)-(g) of the group “D₁” in formula (I) of U.S. Pat. No. 5,484,899,which is incorporated herein by reference.

Preferred azo groups are monoazo and disazo groups. Preferred monoazogroups have the formula

—Ar¹—N═N—Ar²—

wherein Ar¹ is an aryl or heteroaryl group and Ar² is an aryl group.

It is preferred that each aryl group independently is a mono- ordi-cyclic aryl group. Preferred aryl groups are optionally substitutedphenyl and optionally substituted naphthyl. Preferred heteroaryl groupsare pyridonyl and pyrazolonyl.

A first preferred monoazo group is of the Formula (IX) (or saltthereof):

wherein:

Ar¹ is an aryl group, preferably a benzene or naphthalene nucleus;

R³, or each R³ independently, is C₁₋₄ alkyl, nitro, halo or sulphonicacid or a salt thereof;

c is zero or 1 to 4;

R⁴, or each R⁴ independently, is a sulphonic acid or a salt thereof; and

d is 1 or 2;

and is more preferably of the formula:

wherein each of Ar¹, R³ and a are as defined above, R⁴ is sulpho and cis zero or 1.

Ar¹ is preferably optionally substituted phenyl or naphthyl, especiallya phenyl or naphthyl group having at least one sulpho substituent.Further optional substituents which may be present on Ar include ahalogen atom, especially chlorine; an alkyl radical, especially C₁₋₄alkyl, more especially methyl; an acylamido radical, especiallyacetylamino, benzamido or sulphonated benzamido; amino; hydroxy; and analkoxy radical, especially C₁₋₄ alkoxy, more especially methoxy.

As examples of phenyl groups having at least one sulpho substituentthere may be mentioned 2-, 3- or 4-sulphophenyl; 2-sulpho-4-nitrophenyl;2-sulpho-5-nitrophenyl; 4-sulpho-2-methylphenyl;5-sulpho-2-methylphenyl; 2-sulpho-4-methylphenyl;5-sulpho-2-methoxyphenyl; 2-sulpho-4-methoxyphenyl;4-sulpho-2-chlorophenyl; 5-acetamido-2-sulphophenyl;5-sulpho-2-carboxyphenyl; 2,4-disulphophenyl; 2,5-disulphophenyl; and3,5-disulphophenyl.

As examples of naphthyl groups having at least one sulpho substituentthere may be mentioned 1-sulphonaphth-2-yl; 1,5-disulphonaphth-2-yl;1,5,7-trisulphonaphth-2-yl; 3,6,8-trisulphonaphth-2-yl;5,7-disulphonaphth-2-yl; 6-sulphonaphth-2-yl; 4-,5-,6-, or7-sulphonaphth-1-yl; 4,8-disulphonaphth-1-yl; 3,8-disulphonaphth-1-yl;2,5,7-trisulphonaphth-1-yl; and 3,5,7-trisulphonaphth-1-yl.

Preferred optional substituents which may be present on the naphthalenenucleus of Formula (IX) are those mentioned above for Ar¹.

Groups of the Formula (IX) are preferably linked to a group L¹ or L² atthe 6-, 7- or 8-position, especially the 6- or 8-position. When L¹ or L²is to be linked at the 8-position, it is preferred that R⁵ is a sulphogroup at the 5- or 6-position.

Thus a preferred monoazo dye embodying the invention has the formula(XVII)

wherein:

each R independently and a is as defined above;

one of Z³ and Z⁴ is a group Z¹ and the other is a group Z²;

the group Z⁴ is selected from the groups of the formulae (I)-(III),given and defined above.

Ar¹ is a benzene or naphthalene nucleus;

R³, or each R³ independently, is C₁₋₄ alkyl, nitro, halo or sulphonicacid or salt thereof;

c is zero or 1-4;

R⁴, or each R⁴ independently, is a sulphonic acid or a salt thereof; and

d is 1 or 2.

A preferred disazo group is of the Formula (XI) (or salt thereof):

Ar¹—N═N—M—N═N—E  (XI)

wherein:

M and E are each independently optionally substituted phenylene ornaphthalene; and

Ar¹ is as defined above.

It is preferred that E is optionally substituted naphthalene and M isoptionally substituted phenylene. The optional substituents which may bepresent on M or E are preferably independently selected from halo,especially chloro; alkoxy, especially C₁₋₄ alkoxy; alkyl, especiallymethyl; sulpho; carboxy; hydroxy; amino; acylamino, especiallyacetamido, benzamido and sulphonated benzamido, and pyrimidinylamino ortriazinylamino cellulose-reactive groups.

As Examples of groups represented by M and E, there may be mentionedphenylene, 2-methyl-1,4-phenylene, sulphophenylene, ureidophenylene,7-sulpho-1,4-naphthalene, 6-sulpho-1,4-naphthalene;8-sulpho-1,4-naphthalene and 6-hydroxy-4-sulpho-1,5-naphthalene.

An especially preferred range of disazo-dyes has the formula (XVIII)

wherein:

one of Z⁵ and Z⁶ is a group Z¹ and the other is a group Z²;

each of f and g independently is zero or 1;

when Z⁵ or Z⁶ is any of the groups of the formulae (I)-(III), given anddefined above, f or g respectively is 1 and when Z⁵ or Z⁶ is any of thegroups of the formulae (IV)-(VI), given and defined above, f or grespectively is zero;

each of c and e, independently, is zero or 1-4;

d is 1 or 2;

each R independently is as defined above;

each of Ar¹ and Ar² independently is an optionally substituted arylgroup; and

each of R³ and R⁴ is as defined above.

In a dye of the formula (XVIII), each of Z⁵ and Z⁶ may be the same group

wherein X, Y and n are as defined above.

Alternatively, one of Z⁵ and Z⁶ may be a group of the formula (I), givenand defined above, and the other of Z⁵ and Z⁶ may be selected fromgroups of the formulae (II) and (III), given and defined above. In sucha dye it is preferred that one of Z⁵ and Z⁶ is a group of the formula(I), given and defined above, and the other of Z⁵ and Z⁶ is a group ofthe formula (II).

Another especially preferred range of disazo dyes has the formula

wherein:

B is a hydrocarbon bridging group as defined above, and preferably anoptionally substituted aryl group;

one of G¹ and G² is OH and the other is NH₂;

each of X, Y, Y¹, Ar¹, Ar², R³, R⁴, R⁵, c, d and e is as defined above.

In a dye of the formula (XVIII), one of Z⁵ and Z⁶ may be a group

wherein:

X, Y and n are as defined in claim 1 and the other of Z⁵ and Z⁶ is thegroup —SO₂CH₂CH₂OSO₃H or —SO₂CH═CH₂.

Typically such a dye has the formula

wherein

G³ is C₂H₄OSO₃H or a salt thereof or —CH═CH₂;

G¹ and G² are as defined above;

R⁴ and d are as defined above; and

each of h and i, independently, is zero, 1 or 2.

A more preferred range of such dyes has the formula

where each of G¹ G² and G³ is as defined above.

When the chromophore D is an anthraquinone, a preferred anthraquinonegroup is of the Formula (XII) (or a salt thereof).

wherein the anthraquinone nucleus optionally contains a sulphonic acidgroup in the 5-, 6-, 7-, or 8-position and V is a divalent organiclinking group, preferably of the benzene series.

V is a bridging group B, preferably phenylene, diphenylene, or4,4′-divalent stilbene or azobenzene radicals which are optionallysulphonated. It is preferred that V contains one sulphonic acid groupfor each benzene ring present therein.

A preferred anthraquinone dye of has the formula

D^(A)—L³—Ar—L²—Z²—L¹—Z¹

wherein:

D^(A) is an anthraquinone chromophore;

L³ is a linking of the formula (VII)¹, given and defined above;

Ar is an optionally substituted aryl group; and

each of Z¹, Z², L¹ and L² is as defined above.

More preferably each of L¹ and L² independently, is a linking group ofthe formula (VII)¹, (VII)² or (VII)³, given and defined above; and stillmore preferably, each of L¹ and L², independently is a group of theformula (VII)³, given and defined above, in which B is an optionallysubstituted aryl group.

When the chromophore D is a phthalocyanine, a preferred phthalocyaninegroup is of the Formula (XIII) (or a salt thereof).

wherein Pc is a metallo-phthalocyanine nucleus, preferably copper ornickel phthalocyanine; L is as hereinbefore defined; each Windependently is a hydroxy or a substituted or unsubstituted aminogroup, V¹ is a divalent organic linking group, preferably aC₁₋₄-alkylene or phenylene linking group; and a and b are eachindependently 1, 2 or 3 provided that a+b is not greater than 4.

Preferably such a metal phthalocyanine dye has the formula

wherein:

Cu Pc is a copper phthalccyanine chromophore;

x+y+z≦4;

each of R²¹ and R²³, independently is hydrogen or optionally substitutedC₁₋₄alkyl;

B is a hydrocarbon bridging group; and

Z¹ Is as defined above.

When the chromophore D is a triphenodioxazine a preferredtriphenodioxazine group is of the Formula (XIV) (or a salt thereof).

wherein:

each Y¹ independently is a covalent bond, C₂₋₄-alkylene phenylene orsulphophenylene;

U¹ is H or SO₃H; and

T¹ and T² are halo, especially chloro, C₁₋₄-alkyl, or alkoxy.

Each Y³ is preferably —C₂H₄— or —C₃H₆—, U¹ is preferably SO₃H and T¹ andT³ are preferably Cl, methyl or ethyl.

Preferably such a triphendioxazine dye has the formula

Z¹—L¹—[Z³—L³]_(q) —D^(T)—[Z⁴]_(r)—L²—Z²

wherein:

D^(T) is a triphendioxazine chromophore; each of L², L³ and L⁴,independently, is a linking group of the formula (VII)¹, (VII)² or(VII)³, given and defined above;

each of Z², Z³ and Z⁴ is a reactive group selected from groups of theformulae (I)-(III), given and defined above;

each of q and z is zero or 1; and

each of Z¹ and L¹ is as defined above.

In such a dye, Z² is preferably a group of the formula (I), given anddefined above and each of Z³ and Z⁴ is a group of the formula (II),given and defined above; and each of L¹, L², L³ and L⁴ is preferably agroup of the formula (VII)³, given and defined above.

When the chromophore D is a formazan, a preferred group is of theFormula (XV) (or a salt thereof).

wherein:

X¹ is H, SO₃H or Cl; and

each r independently has a value of 0, 1 or 2.

provided that the formazan group has at least one, and preferably atleast two, sulpho groups.

It is preferred that each r has a value of 1.

Preferably such a formazan dye has the formula

[Z^(A)]_(a)—D^(F)—L—Z^(B)—L¹—Z¹

wherein:

D^(F) is a formazan chromophore;

one of Z^(A) and Z^(B) is a group Z², given and defined above;

each of L³ and L⁴ is a linking group of the formula (VII)¹, (VII)² or(VII)³, given and defined above;

each of Z¹ and L¹ is as defined above;

α is zero or 1;

Z^(A) is selected from groups of the formulae (IV)-(VI), given anddefined above; and

Z^(B) is selected from groups of the formulae (I)-(III); given anddefined above.

According to one process aspect, the invention provides a process forpreparing a dye of the formula

Z²—L¹—D—L²—Z²  (VIII)¹

wherein:

D is a chromophore;

each of L¹ and L² independently, is N(R);

each R, independently, is hydrogen or C₁₋₄alkyl;

each of Z¹ and Z² is a group

in which:

n is 1 or 2

X_(n) or each X independently, is an electron withdrawing group; and

Y is a halogen atom, which process comprises reacting a chromophoriccompound of the formula (XX)

H(R)N—D—N(R)H  (XX)

wherein each of D and R is as defined above, with at least two moles,per mole of the chromophoric compound of the formula (XX), of adihalobenzene component comprising at least one dihalobenzene compoundof the formula (XXI)

wherein each of X, Y and n is as defined above, to obtain the dye of theformula (VIII)¹.

When the dye is of the formula (XVIII) given above, the chromophoriccompound of the formula (XX) can be prepared by protecting one aminogroup of a phenylene diamine sulphonic acid and then diazotising thisand coupling a first portion of the diazotised phenylene diaminesulphonic acid to the naphthalene nucleus under acid conditions so as tocouple or, to the benzene ring of the naphthalene nucleus containing anamino group and then taking a second portion of the same diazotised andprotected phenylene diamine sulphonic acid compound referred to above(or a different such compound) and coupling this under neutral oralkaline conditions to the benzene ring of the naphthalene nucleuscontaining a hydroxyl group to obtain a diamine dyestuff havingrespective protected amino groups. The protective group can then beremoved by hydrolysis.

According to another process aspect, the invention provides a processfor preparing a dye of the formula (VIII)¹

Z¹—L¹—D—L²—Z²  (VIII)²

wherein:

D is a chromophore;

each of L¹ and L² independently, is N(R);

each R, independently, is hydrogen or C₁₋₄alkyl;

Z¹ is a group

in which:

n is 1 or 2

X, or each X independently, is an electron withdrawing group; and

Y is a halogen atom; and

Z² is selected from the groups (II) and (III) defined above;

which process comprises reacting a chromophoric compound of the formula(XX)

H(R)N—D—N(R)H  (XX)

wherein each of D and R is as defined above, with one mole, per mole ofthe chromophoric compound of the formula (XX), of each of

(a) a dihalobenzene compound of the formula (XXI)

wherein each of Z, X, Y and n is as defined above; and

(b) a compound selected from

wherein:

m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2, D is 0;

Y², or each Y¹ independently, is a halogen atom or an optionallysubstituted pyridinium group; and

T is C₁₋₄alkoxy, C₁₋₄thioalkoxy or N(R¹)(R²), in which each of R¹ and R²independently is hydrogen, optionally substituted C₁₋₄alkyl oroptionally substituted aryl;

x is 1, 2 or 3; y is zero, 1 or 2; and x+y≦3;

Y², or each Y¹ independently, is a halogen atom or an optionallysubstituted pyridinium group;

U or each U independently, is C₁₋₄alkyl or C₁₋₄alkylsulphonyl; and

Y is as defined above;

the said reactions of the compound of the formula (XX) with each of therespective compounds of the formulae (XII) and (XIII) being carried outsimultaneously or one before the other, in either order, to obtain a ofthe formula (VIII)².

According to yet another process aspect, the invention provides aprocess for preparing a dye of the formula (VIII)³

Z¹—L¹—D—Z²  (III)³

wherein:

D is a chromophore

L¹ is N(R), in which R is hydrogen or C₁₋₄alkyl;

Z¹ is a group

in which n is 1 or 2; X, or each X independently, is an electronwithdrawing group; and Y is a hydrogen atom; and Z² is a group of theformula (IV)

—SO₂ CH₂ CH₂ X¹  (IV)

wherein X¹ is an eliminatable group;

a group of the formula  (V)

—SO₂ (CH₂)_(2 CH═CH) ₂(V)

wherein z is zero or 1; and

a group of formula  (VI)

—W—C(R¹⁰)═CH₂  (VI)

wherein:

R¹⁰ is hydrogen, C₁₋₄alkyl or halogen; and

W is —OC(═O)— or —N(R¹¹)C(═O)— in which R¹¹ is hydrogen or C₁₋₄alkyl;

which process comprises reacting a chromophoric compound of the formula(XXIV)

H(R)N—D—Z²  (XXIV)

wherein D and Z² are as defined above, with a dihalobenzene compound ofthe formula (XXI)

wherein each of X, Y and n is as defined above, to obtain the dye of theformula (VIII)³.

Although dye formulae have been shown in the form of their free acid inthis specification, the invention also includes dyes and processes usingdyes in the salt form, particularly their salts with alkali metals suchas the potassium, sodium, lithium or mixed sodium/lithium salt and theirsalts with tetraalkylammonium ions.

The dyes may be used for dyeing, printing or ink-jet printing, forexample, of textile materials and paper.

The process for colouration is preferably performed at a pH of 7.1 to13, more preferably 10 to 12, pH levels above 7 can be achieved byperforming the process for colouration in the presence of anacid-binding agent.

The substrate may be any of a textile material, leather, paper, hair orfilm, hot is preferably a natural or artificial textile materialcontaining amino or hydroxyl groups, for example textile material suchas wool, silk, polyamides and modified polyacrylonitrile fibres, andmore preferably a cellulosic material, especially cotton, viscose andregenerated cellulose, for example, that commercially available asTencel. For this purpose the dyes can be applied to the textilematerials at a pH above 7 by, for example, exhaust dyeing, padding orprinting, including ink-jet printing. Textile materials are colouredbright shades and possess good fastness to light and wet treatments suchas washing.

The new dyes are particularly valuable for colouring cellulosic textilematerials. For this purpose, the dyes are preferably applied to thecellulosic textile material at a pH above 7 in conjunction with atreatment with an acid binding agent.

Preferred acid-binding agents include alkali metal carbonates,bicarbonates, hydroxides, metasilicates and mixtures thereof, forexample sodium bicarbonate, sodium carbonate, sodium metasilicate,sodium hydroxide and the corresponding potassium salts. The dyes benefitfrom the excellent build-up and high fixation.

At least for cellulosic materials, exhaust dyeing can be carried out ata relatively low temperature about 50-70° C., especially about 60° C.

The new dyes can be applied to textile material containing amine groups,such as wool and polyamide textile materials, from a neutral to mildlyalkaline dyebath. The dyeing process ran be carried out at a constant orsubstantially constant during the dyeing process, or if desired the pHof the dyebath can be altered at any stage of the dyeing process.

The dyes may be in a liquid form, or solid form, for example in granularor powdered form.

We find surprisingly that such dyes give a much higher build up, ascompared with known dyestuffs, particularly in warm dyeing applicationsat about 60° C.

In addition, a wide selection of dye backbones is possible, giving thepotential to provide high fastness dyes.

Dyes embodying the invention are especially useful for application tosubstrates by ink-jet technologies. Substrates which are particularlyuseful are cellulosic textiles and paper.

The dye used in the ink is preferably purified by removal ofsubstantially all the inorganic salts and by-products which aregenerally present in a commercial dye at the end of its synthesis. Suchpurification assists in the preparation of a low viscosity aqueoussolution suitable for use in an ink jet printer.

To assist in the achievement of heavy depths of shades the dye shouldpreferably have a water-solubility of at least 5%, and more preferablyfrom 5% to 25%, by weight. Solubility of the dye can be enhancedconverting the sodium salt, in which form it is normally synthesised,either partially or wholly, into the lithium or ammonium salt.Purification and ion exchange can conveniently be effected by use ofmembrane separation processes which permit the separation of unwantedinorganic materials and by-products directly from an aqueous solution ordispersion of the dye by partial or complete exchange of thecounter-ion. The ink preferably contains, up to 20% by weight of dye andmore preferably from 2% to 10%, especially from 3% to 8%.

The ink may also contain a humectant, which may also function as a watermiscible solvent, which preferably campfires a glycol ordihydroxyglycolether, or mixture thereof, in which one or both hydroxygroups are secondary hydroxy groups, such aspropane-1,2-diol,butane-1,3-diol and3-(3-hydroxy-prop-2-oxy)propan-2-ol.

Where the humectant has a primary hydroxy group this is preferablyattached to a carbon atom adjacent to a carbon atom, carrying asecondary or tertiary hydroxy group. The humectant may comprise up to atotal of 10% by weight of a polyol, especially a glycol ordihydroxyglycolether, having two or more primary hydroxy groups, such asethyleneglycol,propane-1,3-diol,butane-1,4-diol,2-(2-hydroxyethoxy)ethanol and2-(2-[2-hydroxyethoxy)ethanol and/or an alcohol with a primary hydroxygroup, such as ethanol,n-proponol and n-butanol. However, it preferablycontains not more than 5% by weight, and is more preferably free from,such compounds. In the context of the humectant, the term “alcohol”means a compound having only one hydroxy group attached to an aliphaticcarbon atom. The ink preferably contains from 5% to 25%, by weight, moreespecially from 10% to 20%, of humectant.

If desired, the ink may be buffered to a pH from 5 to 8, especially to apH from 6 to 7, with a buffer such as the sodium salt of metanilic acidor an alkali metal phosphate, or di- or triethanolamine.

The ink preferably also contains one or more preservatives to inhibitthe growth of fungi, bacteria and/or algae because these can block thejet of the ink jet printing equipment. Where the ink jet printingtechnique involves the charging and electrically controlled deflectionof drops the solution preferably contains a conducting material such asan ionised salt to enhance the accumulation of charge on the crop.Suitable salts for this purpose are alkali metal salts of mineral acids.The remainder of the ink is preferably water, especially de-ionisedwater to avoid the introduction of impurities into the ink.

Especially preferred embodiments of the invention will now be describedin more detail with reference to the following Examples in which allparts and percentages are by weight unless otherwise stated. Althoughpreparation and dyeing with any single dye is exemplified, particularadvantage could be seen when dyeing with mixtures of dyes.

PREPARATIVE EXAMPLES Example 1

2-amino-4-(N-acetyl)aminobenzene-1-sulphonic acid (0.5M, 182 g) wasdissolved in water (600 ml) at pH 7 and 2M sodium nitrite solution added(0.526M, 263 ml). This solution was added dropwise to a mixture ofhydrochloric acid 35% (1.13M, 100 ml, SG=1.18) and ice (1 Kg),maintaining a temperature of 0-5° C. The mixture was stirred for 0.5 hrswith excess nitrous acid at 0-5° C. A solution of sulphamic acid (10%)was added to remove excess nitrous acid to obtain a suspension of adiazotized diamine for coupling.

H-Acid (0.475M, 183 g) was dissolved in water (600 ml) at PH 7.5. Thissolution was added dropwise to the above diazo suspension with goodagitation over 1 hr at 0-2° C. The mixture was then stirred at 0-2° C.for a further 2 hrs at pH 2-3, and allowed to warm to room temperatureover 18 hrs.

The viscous suspension was adjusted to pH 6 using sodium hydroxidesolution (46/48%) and a solution of a monoazo dye was thereby obtained.

The above monoazo dye solution was cooled to 0-5° C. and a batch of thediazotized diamine prepared as above was added. The mixture was stirredat 0-5° C. and PH 6-7 for 2 hrs and subsequently over 18 hrs at roomtemperature while maintaining the pH at 6-7 using 2M sodium carbonatesolution, thereby obtaining a diazo dye solution.

Hydrolysis was then carried out by adding sodium hydroxide solution(46/48%, 800 g) to the above diazo dye solution (vol=5L) and heating at70-75° C. for 1.5 hrs.

The reaction mixture was Cooled to 20% and neutralised by controlledaddition of 35% hydrochloric acid. After screening to remove a mullamount of impurity sodium chloride was added (15% w/v) and stirringcontinued to allow precipitation of the resultant diaminodisazo product.This was collected by filtration and dried at 40° C. (285 g; 0.242M;strength=69.3%).

The above diaminodisazo dye (0-01M, 11.18 g) was dissolved inwater/acetone (100 ml, 1:1) at 50° C. A solution of1,5-difluoro-2,4-dinitrobenzene (0.023M, 4.7 g taken as 100% strength)in acetone (20 ml) was added over 0.25 hr and the mixture heated at 55°C. for 3 hrs. The pH was maintained at 7 throughout the reaction by theaddition of 2N sodium carbonate solution.

The reaction mixture was cooled to 20° C. and acetone (150 ml) added toprecipitate the dye, The product was collected by filtration and washedwith acetone (50 ml) and dried at 40° C. to give a greenish-navydye(11.12 g; 0.0075M; strength=74.8%) (λ_(Max)=607 nm; ε_(Max)=57,036).

Example 2

The method of Example 1 was followed except that the diaminodisazo wasreacted with 1,5-dichloro-2,4-dinitrobenzene in place of1,5-difluoro-2,4-dinitrobenzene to give a greenish-navy dye (λ_(Max=)607nm; ε_(Max)=48,212).

Example 3

The method of Example 1 was followed except that the diaminodisazo wasreacted with 1,5-difluoro-2-cyan-4-nitrobenzene in place of 1,5-difluoro2,4-dinitrobenzene to give a greenish-navy dye (λ_(Max)=607 nm;ε_(Max)=56,416).

Example 4

The method of Example 1 was followed except that the diaminodisazo wasreacted with 1,5-difluoro-2-nitrobenzene in place of1,5-difluoro-2,4-dinitrobenzene to give a greenish-navy dye (λ_(Max)=608nm; ε_(Max)=54,660).

Example 5

4-Amino benzene sulphatoethylsulphone (0.1 m, 30 g) was stirred inice/water (400 ml) and hydrochloric acid 35% (0.58M, 52 ml, SG=1.18) andthe temperature maintained at below 5° C. 2M sodium nitrite solution(0.104M, 52 ml) was added dropwise at below 5° C. and the mixturestirred for a further 2 hours. A solution of sulphamic acid was added(10%) to remove excess nitrous acid and provide a diazo suspension forcoupling.

H-Acid (0.103M, 42.6 g) was dissolved in water (300 ml) at pH 6 and thesolution cooled to 5° C. This solution was added dropwise to the abovediazo, suspension with good agitation, while maintaining the temperaturebelow 5° C. The mixture was then stirred for 18 hours, allowing thetemperature to rise to 20° C. Sodium chloride (10% w/v) was added andthe mixture stirred for 1 hour. The precipitated monoazo dye wascollected by filtration and reslurred in ethanol (600 ml) for 1 hour at20° C. The product was collected by filtration and dried at 40° C. (70g; 0.0825M; strength=72%).

3-Amino-5′-fluoro-2′,4′-dinitrodiphenylamine-4-sulphuric acid (0.0068M,3.2 g) was dissolved in water (100 ml) at 50-60° C. and the solutioncooled to 20° C. 2M Sodium nitrite solution (0.008M, 4 ml) was added andthe mixture cooled to 0-2° C. and added dropwise to ice (50 g) andhydrochloric acid 35% (0.09M, 8 ml), while maintaining the temperatureat 0-2° C. the resulting yellow suspension was stirred at 0-20° C. for0.5 hour and a solution of sulphamic acid (10%) added to remove excessnitrous acid and provide a diazo suspension for coupling.

The diazo suspension Was then added dropwise to a solution of the abovemonoazo dye (0.006M, 5.1 g) in water (150 ml) at pH 5 and 0-2° C. The pHof the coupling mixture was maintained at pH 5 by the addition of 2Msodium carbonate solution and stirred at this pH for 18 hours, allowingthe temperature to rise to 20° C. Sodium chloride was added (20% w/v)and the product collected by filtration. The solid was reslurried inethanol (100 ml) for 1 hour at 20° C. collected by filtration and driedat 40° C. to obtain a greenish-navy dye (4.4 g: 0.003M; strength=67%;(λ_(Max)=608 nm; ε_(Max=)54,279) of the structure given below:

Examples 6-61

Other diazo naphthalene structures embodying the invention are shown asExamples 6 to 61 in Table 1. They can be prepared by methods analogousto those outlined in Examples 1 to 5.

Examples 62-67

Still further diazo naphthalene dyes embodying the invention, in whichthe chromophore has been doubled up via a linking group, are shown inExamples 62 to 67 in Table 2.

Example 68

This Example describes how a dye may be synthesised where thefibre-reactive halobenzene group is attached via a linking diamine to asecond fibre-reactive group, and thereby to a chromophore.

The N-diachlorotriazinyl derivative of the azo dye resulting fromazo-coupling 7-aminonaphthalena-1,3,6-trisulphonic acid withm-ureidoaniline was prepared by conventional means. A solution of thisdye (35 mmol in 450 ml) was added at room temperature with stirring toN-(4-aminophenyl)piperazine (7.5 g, 42 mmol) dissolved in 50/50acetone/water (400 ml) maintained at pH 6-6.5 by addition of sodiumcarbonate solution. After completion of the reaction the solution wasconcentrated, and the product was precipitated by addition of methylatedspirit. To a solution of this intermediate (8.4 of mmol) in 50/50acetone/water (200 ml) was added a solution of1,5-difluoro-2,4-dinitrobenzene (8.5 mmol) in acetone (20 ml),maintaining the pH at 8.5 by of sodium carbonate solution. On completionof the reaction, the pH was adjusted to 6.5 and the solution wasconcentrates ca 100 ml. Methylated spirit was added, and the product dyewas filtrated, washed with meths and dried. λ_(max)(water)=379 nm,ε_(max)=33000 l mol⁻¹ cm⁻¹, half band width >150 nm. This material dyedcotton a bright golden yellow shade with very good fastness properties.

Examples 69-77

By following the principles described in Example 68, dyes of a similarnature may be prepared as further exemplified by dyes 69-77 listed inTable 3.

Examples 78-97

Disazo naphthalene dyes containing two reactive groups attached to thechromophore as described in Example 68 are exemplified by Examples 76 to97 listed in Table 4.

Examples 98-127

Further yellow dyes may be prepared by the methods described in Examples1-6 and 68, and are listed in Tables 5 to 9.

Examples 128-160

Monoazo naphthalene dyes embodying the invention are listed in Tables 10to 12.

Examples 161-189

A variety of dyes embodying the invention, containing blue and greenchromophores, are listed in Tables 13 to 16.

APPLICATION EXAMPLES Examples 190-192

Each of the dyes (0.2 parts) of respective Examples 1, 3 and 5 wasdissolved in respective amounts of water (50 parts) at 25° C. and pH 9.Cotton fabric 5 parts) and Glaubers salt (2.5 parts) were added. Thedyes were fixed to the cotton by raising the temperature to between 50°C.-60° C., basifying to pH 11.0 and maintaining this for 1 hr. Thecotton was removed and washed in soapy water to give a darkgreenish-navy cotton having high general fastness properties.

Examples 193 and 194

Each of the dyes (0.2 parts) of respective Examples 2 and 4 wasdissolved in water (50 parts) at 25° C. and pH 9. Cotton fabric (5parts) and salt (4 parts) were added. The dyes were fixed to cotton byraising the temperature to 80-100° C. and maintaining this for 1 hr. Thecotton was removed and washed in soapy water to give a deepgreenish-navy cotton having good tastness properties.

Examples 195-198

Methodology for applying dyes embodying the present invention to cottonmay be further exemplified by means of the following pad-batch dyeingprotocol.

Example 195-198

Example 195. Dye from Example 5 (0.5 parts) was dissolved in water (30parts) at 25° C. and the following agents were added: Primasol NF (1part of 20% solution) and sodium silicate Q70 (9.5 part of 50%solution), sodium hydroxide (5.1 parts of 10% solution). The solutionwas made up to 50 parts by addition of water, and then padded onto wovencotton fabric (70% pick-up). The cloth to wrapped in cling film andbatched at room temperature for 24 hours. The cling film was removed andthe dyed cloth was rinsed successively with cold water and hot water,then washed with a soap solution, rinsed with water, and dried to givecotton coloured a dull greenish blue shade.

Example 196. If the amount of dye used in Example 193 is doubled and theprocedure repeated, a greenish-navy shade is obtained.

Example 197. If the amount of dye used in Example 193 is trebled and theprocedure repeated, a dark navy shade is obtained.

Example 198. If six times the amount of dye in Example 193 is used andthe procedure repeated, an almost black shade is obtained.

Other dyes from the above Examples, particularly those containing the2,4-dinitrofluorobenzene unit and/or a vinyl sulphone group or itssulphate half-ester precursor, can be applied to cotton by the samemethod.

Example 199

Dyes embodying the present Invention may be applied to textilesubstrates, especially cotton, by conventional printing technology, asthe following exemplifies.

A dye from Example 5 (30 parts) was dissolved in a solution containingManutex F 700 (500 parts of a 10% solution) and Vitexol D (20 parts).The solution was made up to 1000 parts by the addition of water andprinted by means of a Zimmer screen printer. The printed cloth was driedand padded through a solution containing sodium silicate (48edge, 700parts) made up to 1000 parts by the addition of water (80% pickup).Immediately after padding, the printed cotton was steamed in a RoachesFlash-ager steam chamber at 120 deg C. for 45 seconds. The printed clothwas rinsed in cold water, washed with a soap solution at the boil,rinsed again in cold water and dried to give a dull greenish navy printon the cotton.

Example 200

Dyes embodying the present invention may be used in the preparation ofinks specially formulate for application by ink-jet technology. As anExample, the dye from Example 5 (6 parts) was dissolved in a solution ofpropylene glycol (15 parts) and water (79 parts). When this solution wasapplied to cotton which had previously been pretreated (for example,with a pretreatment agent described in E2-A-0534660) by means ofcommercial ink-jet printing equipment, deep navy shades were obtained.

Other dyes from the above examples as well as others described by theInvention may be used to prepare inks suitable for ink-jet printing.

Example 201

Reactive dyes, including those of Examples 1-189, are usually isolatedas their sodium salts, and are contaminated with inorganic impuritiesresulting from the method of preparation. Dyes free of impuritiessuitable for ink let printing, and/or with increased solubility, may beprepared by conventional ion exchange techniques, where for examplesodium is replaced by lithium and inorganic impurities aresimultaneously removed.

Dye from Example 1 (10 parts) was dissolved in water (100 parts) andtreated on a reverse osmosis rig until permeate conductivity was 10micro reciprocal ohms. A solution of lithium chloride was added to thedye solution and treatment on the r.o. rig was continued until thepermeate conductivity had to decreased to 1 micro reciprocal ohm, Thesample was concentrated to a volume of about 80 parts, after which thesolution was buffered and other formulating agents were added. The dyesolution was then diluted to 90 parts by addition or water, at whichstage it was suitable for storage. Dye solution prepared in this waycould be diluted and applied to cotton by the methods described in anyof the Examples 190, 195-198, or formulated into an ink by addition ofsuitable humectants and/or cosolvents, and applied by ink-jetmethodology to cotton, for example by the method described in Example200. In all these cases, dull blue, greenish navy of black, shades wereimparted to the substrate, depending on the amount of dye applied.

Example 202

Dye from Example 1 was ion exchange to the lithium form as in Example201, and formulated into an ink with the composition: dye (5 parts),propylene glycol (12 parts), diethanolamine (sufficient to buffer thefinal pH to 7-8.5), and water (to bring the total to 100 parts). The inkwas added to the ink reservoir of an ink jet printer (e.g. HP Desk Jet500) and printed onto paper (Logic 300), to give a black print ofgenerally good fastness properties.

TABLE 1

λ_(max) nm (w _(1/2) nm) Colour on Example A B cotton 6

606 (121) greenish-navy 7

607 (105) greenish-navy 8

623 (121) dark bluish-green 9

616 (121) greenish-navy 10

603 (105) greenish-navy 11

618 (130) greenish-navy 12

614 (110) dark bluish-green 13

594 (112) greenish-navy 14

595 (108) greenish-navy 15

604 (110) dark bluish-green 16

645 (137) very dull dark green 17

604 (119) greenish-navy 18

603 (127) greenish-navy 19

600 (134) greenish-navy 20

596 120) greenish-navy 21

609 (111) greenish-navy 22

604 (120) greenish-navy 23

625 (104) greenish-navy 24

620 (112) drak bluish-green 25

632 (114) dark bluish-green 26

609 (141) dark bluish-green 27

602 (125) greenish-navy 28

605 (143) dark blusish-green 29

596 (129) greenish-navy 30

607 (109) greenish-navy 31

595 (107) greenish-navy 32

622 (123) greenish-navy 33

619 (114) dark bluish-green 34

606 (114) dark bluish-green 35

618 (113) dark bluish-green 36

616 (110) dark bluish-green 37

616 (106) greenish-navy 38

616 (111) dark bluish-green 39

608 (111) greenish-navy 40

608 (110) greenish-navy 41

608 (116) greenish-navy 42

616 (111) dark bluish-green 43

615 (120) dark blusish-green 44

615 (118) dark bluish-green 45

greenish-navy 46

dark bluish-green 47

greenish-navy 48

dark bluish-green 49

greenish-navy 50

dark bluish-green 51

greenish-navy 52

dark bluish-green 53

dark bluish-green 54

greenish-navy 55

dark bluish-green 56

dark bluish-green 57

greenish-navy 58

greenish-navy 59

dark bluish-green 60

dark bluish-green 61

greenish-navy

TABLE 2

λ_(max) nm (w_(1/2) nm) Colour on Example A B cotton 62

609 (118) dull dark green 63

608 (112) dull dark green 64

630 (130) dull dark green 65

Greenish-navy 66

Greenish-navy 67

Greenish-navy

TABLE 3

Colour on Example L λ_(max) nm w _(1/2) nm cotton 69

415 139 Golden yellow 70

307 140 Golden yellow 71

403 200 Golden yellow 72

419 200 Golden yellow 73

366 119 Golden yellow 74 NHC₂H₄NH 410 170 Golden yellow 75

378 155 Golden yellow 76

389 150 Golden yellow 77

360 160 Golden yellow

TABLE 4

Example A B X Y Colour on cotton 78

NH₂ OH Greenish navy 79

OH NH₂ Greenish navy 80

NH₂ OH Greenish navy 81

OH NH₂ Greenish navy 82

NH₂ OH Greenish navy 83

OH NH₂ Greenish navy 84

NH₂ OH Greenish navy 85

OH NH₂ Greenish navy 86

NH₂ OH Greenish navy 87

OH NH₂ Greenish navy 88

NH₂ OH Greenish navy 89

OH NH₂ Navy 90

NH₂ OH Navy 91

OH NH₂ Greenish navy 92

NH₂ OH Greenish navy 93

OH NH₂ Greenish navy 94

OH NH₂ Greenish navy 95

NH₂ OH Greenish navy 96

OH NH₂ Greenish navy 97

OH NH₂ Greenish navy

TABLE 5

Example Structure λ_(max) nm w_(½)nm Colour on cotton 98 Dye-SC₂H₄OH 407148 Golden yellow 99 Dye-N(CH₃)Ph 403 138 Golden yellow 100Dye-NHC₂H₄SO₃H 407 129 Golden yellow 101 Dye-NHC₂H₄OC₂H₄OH 412 134Golden yellow 102 Dye-NHC₆H₃-m-SO₃H 409 143 Golden yellow 103Dye-NHC₂H₄NH-Dye Golden yellow 104

412 130 Golden yellow

TABLE 6

Colour on Example Structure λ_(max) nm w_(½)nm cotton 105 Dye-SC₂H₄OH437 151 Mid yellow 106

430 135 Mid yellow 107 Dye-NHC₂H₄OC₂H₄OH 436 141 Mid yellow 108

435 132 Mid yellow 109

439 143 Mid yellow 110

438 149 Mid yellow 111

437 131 Mid yellow 112 Dye-NHC₂H₄NH-Dye Mid yellow 113 Dye-NHC₃H₆NH-DyeMid yellow

TABLE 7 λ_(max) nm Ex- (w_(1/2) nm) am- Colour on ple Structure cotton114

435 (172) mid yellow 115

422 (148) golden yellow 116

406 (124) golden yellow

TABLE 8

Example

Other Substituents Colour on cotton 117 4- 1,3-(SO₃H)₂ 3-SO₂C₂H₄OSO₂HYellow 118 3- 1,4-(SO₃H)₂ 2′-SO₂C₂H₄OSO₃H Yellow 119 4- 1,1′-(SO₃H)₂Yellow

120 4- 1,1′-(SO₃H)₂ Yellow

121 4′- 1,1′,4-(SO₃H)₃ Yellow

TABLE 9

Colour on Example A B X Y cotton 122

H H Greenish- yellow 123

H CN Greenish- yellow 124

H CONH₂ Greenish- yellow 125

C₂H₄OH H Greenish- yellow 126

C₂H₄OH CONH₂ Greenish- yellow 127

H H Greenish- yellow

TABLE 10

Colour on Example A B X Y cotton 128

SO₃H H Bluish red 129

SO₃H H Bluish red 130

H SO₃H Bluish red 131

SO₃H H Bluish red 132

SO₃H H Bluish red 133

H SO₃H Bluish red 134

SO₃H H Bluish red 135

SO₃H H Bluish red 136

SO₃H H Bluish red 137

H SO₃H Bluish red 138

SO₃H H Bluish red

TABLE 11

Colour on Example A B X cotton 139

H Red 140

SO₃H Red 141

H Red 142

SO₃H Red 143

H Red 144

SO₃H Red 145

SO₃H Red 146

SO₃H Red 147

H Red 148

H Red 149

SO₃H Red

TABLE 12

Colour on Example A B X Y cotton 150

H H Reddish yellow 151

H SO₃H Reddish yellow 152

Me H Reddish yellow 153

H H Reddish yellow 154

H H Orange 155

H SO₃H Orange 156

Me H Orange 157

H H Orange 158

H H Orange 159

H SO₃H Orange 160

Me H Orange

TABLE 13

Colour on Example A cotton 161

Greenish blue 162

Greenish blue 163

Greenish blue 164

Greenish blue

TABLE 14

Colour on Example R R′ R″ x y z cotton 165

H H 2 0 2 Green 166

H H 1.5 0.5 2 Green 167 C₂H₄ H H 2 0 2 Bluish- green 168 C₃H₆ CH₃ CH₃1.7 0.3 2 Bluish- green 180

H C₂H₄OSO₃H 2.5 0.5 1 Green 170

H H 1.5 1.5 1 Green 171

H C₂H₄SO₃H 2.5 0 1.5 Green 172

H H 3 0 1 Green

TABLE 15

Example A B X Y Colour on cotton 173

Cl Cl Blue 174

Cl Cl Blue 175

Cl Et Blue 176

Cl Cl Greenish blue 177

Cl Et Greenish blue 178

Cl Cl Greenish blue 179 H

Cl Cl Greenish blue 180

Cl Me Blue 181

Cl Cl Greenish blue

TABLE 16

Colour on Example A X cotton 182

H Dull greenish blue 183

H Dull greenish blue 184

H Dull greenish blue 185

H Dull greenish blue 186

H Dull blue 187

H Dull greenish blue 188

3-SO₃H Dull greenish blue 189

4-SO₂C₄H₆OSO₃H Dull greenish blue

What is claimed is:
 1. A dye comprising at least one chromophore D; atleast a first, halobenzene, reactive group Z¹, of the formula (I)

wherein: n is 1 or 2; X, or each X independently is an electronicwithdrawing group; and Y is a halogen atom; at least a second reactivegroup Z² selected from the group consisting of: a group of the formula(IV) —SO₂CH₂CH₂X¹  (IV) wherein X¹ is an eliminatable group; and a groupof the formula (V) —SO₂(CH₂)_(z)CH═CH₂  (V) wherein z is zero or 1; atleast a first linking group L³, linking said first, halobenzene,reactive group Z¹ to one of components (i) a chromophore D and (ii) thesecond reactive group Z², which said first linking group L³ presents anamino nitrogen to the reactive group Z¹ and to the component (i) or,when component (i) contains a heterocyclic nitrogen atom, is linkeddirectly to the nitrogen atom and which said first linking group L¹optionally includes a hydrocarbon bridging group, which hydrocarbonbridging group B has at least two carbon atoms, is optionallysubstituted, optionally includes at least one hetero atom and isoptionally a chromophore; and optionally at least one aromatic group Arwhich may carry the said reactive group Z²; which dye is selected fromthe group consisting of dyes of the formulae (VIII), (XXX), (XXXI),(XXXII), (XXXVI) and (XXXVII), wherein: formula (VIII) is: Z^(1—L)¹¹—D—Z²  (VIII) wherein: D is a chromophore; L¹¹ is a group of L¹, whichis an amine or piperazine linkage of the formula —N(R)—  (VII)¹;

wherein: R, or each R independently, is hydrogen or optionallysubstituted C₁₋₄alkyl; B is a hydrocarbon bridging group which has atleast two carbon atoms, is optionally substituted, optionally includesat least one hetero atom and is optionally a chromophore; b is from 2 to6 inclusive; and each of Z¹ and Z² is as defined above; formula (XXX)is: Z¹—L¹—D[L³]_(q)—[Z³—L⁴]_(r)[J¹]_(s)Z²  (XXX) wherein: Z³ is a thirdreactive group selected from the groups of the formulae (I)-(III),wherein: formula (I) is given and defined above; formula (II) is

wherein: m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2,p is 0; Y¹, or each Y¹ independently, is a halogen atom or an optionallysubstituted pyridinium group; and T is C₁₋₄ alkoxy, thioalkoxy orN(R¹)(R²) in which R¹ is hydrogen, optionally substituted C₁₋₄ alkyl oroptionally substituted aryl; and formula (III) is

wherein: X is 1, 2 or 3; y is zero, 1 or 2; and x+y≦3; Y², or each Y²independently, is a halogen atom or an optionally substituted pyridiniumgroup; and U, or each U independently, is C₁₋₄ alkyl or C₁₋₄alkylsulphonyl; J¹ is an optionally substituted aryl group or achromophore; L³ is a linking group linking one of Z³ and J¹ to D; L⁴ isa linking group linking Z³ and J¹; each of q, r and s independently, iszero or 1; and each of Z¹, Z² and L² is as defined above; formula (XXXI)is: Z¹—L¹—D¹[L³—Z³(L⁴—Z⁴)₁L⁵—D²]_(k)Z²  (XXXI) wherein: D¹ is a firstchromophore; D² is a second chromophore; Z³, when present, is a thirdreactive group selected from the groups of the formulae (I)-(III), givenand defined above; Z⁴, when present, is a fourth reactive group selectedfrom the groups of the formulae (I)-(III), given and defined above; L³ 3is a linking group linking Z³ to D¹; L⁴ is a linking group linking Z³ toZ⁴; L⁵ is a linking group linking D² to one of Z³ and Z⁴; each of k andl, independently, is zero or 1; and each of Z¹, Z² and L¹ is as definedabove; formula (XXXII) is: Z¹—L¹—Z³—L³—D—Z²  (XXXII) wherein: Z³ is athird reactive group selected from the groups (I)-(III), given anddefined above and L³ is a third linking group selected from the groups(VII)¹, (VII)² and (VII)³, given and defined above; Z² is a secondreactive group selected from the groups (IV)-(V), given and definedabove; and each of Z¹ and L¹ is as defined above; formula (XXXVI) is:

wherein: one of Z³ and Z⁴ is a reactive group Z² selected from theformulae (IV) and (V) given and defined above; the other of Z³ and Z⁴,independently, is a reactive group selected from the formulae (IV) and(V), given and defined above, and formula given and defined below; eachof t and u, independently, is zero or 1 and at least one of t and u is1; when Z³ is a reactive group Z², t is 1 and when Z⁴ is a reactivegroup Z², u is 1; D is a chromophore; Ar is an optionally substitutedaryl group; L¹ is a group of the formula (XLI)

wherein B and each R, independently, is as defined above; Z¹ is a groupof the formula (I), given and defined above; and wherein: formula (VI)is —W—C(R¹⁰)═CH₂(VI) wherein: R¹⁰ is hydrogen, C₁₋₄alkyl or halogen; andW is —OC(═O)— or —N(R¹¹)C(═O)— in which R¹¹ is hydrogen or C₁₋₄alkyl;and formula (XXXVII) is: Z¹—L¹—D^(N)—Z²  (XXXVII) wherein: D^(N) is achromophore containing a heterocyclic group including a nitrogen atom;L¹ is a group of the formula (VII)⁴ or (VII)⁵,

wherein B is a hydrocarbon bridging group which has at least two carbonatoms, is optionally substituted, optionally includes at least onehetero group and is optionally a chromophore, R is hydrogen or C₁₋₄alkyl and b is from 2 to 6 inclusive; which group of the formula (VII)⁴or (VII)⁵ is directly attached via the bond {circle around (1)}, to thenitrogen atom of the said chromophore D^(N); and each of Z¹ and Z² is asdefined above.
 2. A dye according to claim 1, wherein the linking groupL¹ has the formula (VII)¹ N(R)  (VII)¹ wherein R is hydrogen oroptionally substituted C₁₋₄ alkyl, such that the same amino grouppresents itself to each of the reactive group Z¹ and the component (i),as defined in claim
 1. 3. A dye according to claim 1, wherein thelinking group L³ is a piperazinoalkylamino group of the formula (VII)²

wherein each R, independently, is hydrogen or optionally substitutedC₁₋₄ alky, such that the same amino group presents itself to each of thereactive group Z¹ and the component (i), as defined in claim
 1. 4. A dyeaccording to claim 1, wherein the linking group L¹ has the formula(VII)³ —N(R)BN(R)—  (VII)³ wherein B is a hydrocarbon bridging group asdefined in claim 1, each R, independently , is as defined in claim 1 andB is optionally linked additionally to at least one additional group—N(R).
 5. A dye according to claim 4, wherein the hydrocarbon bridginggroup B is an optionally substituted aryl group.
 6. A dye according toclaim 1, of the formula (VIII) Z¹—L¹¹—D—Z²  (VIII) wherein: D is achromophore; L¹¹ is a group of L¹ which is an amine or piperazine,linkage of the formula

wherein; R, or each R independently, is hydrogen or C₁₋₄ alkyl; B is ahydrocarbon bridging group which has at least two carbon atoms, isoptionally substituted, optionally includes at least one hetero atom andis optionally a chromophore; b is from 2 to 6 inclusive; Z¹ is a group

in which: n is 1 or 2; X, or each X independently, is an electronwithdrawing group; and Y is a halogen atom; and Z² is:—SO₂CH₂CH₂X¹  (IV) in which X¹ is an eliminatable group; or—SO₂(CH₂)_(z)CH═CH₂  (V) wherein z is zero or
 1. 7. A dye accordingclaim 1, wherein, in formula (I), X, or each X independently, isselected from nitro, cyano, alkylsulphonyl, dialkylaminosulphonyl andsulphonic acid or a salt thereof.
 8. A dye according to claim 2, whereinR, or each R independently, ie hydrogen.
 9. A dye according to claim 1,wherein D is an azo chromophore.
 10. A dye according to claim 9, whereinD is a monoazo chromophore.
 11. A dye according to claim 10, which hasthe formula (XVII)

wherein: R is halogen, optionally substituted C₁₋₄ alkyl or optionallysubstituted aryl; Z¹ is of the formula (I); wherein formula (I) is

wherein: n is 1 or 2; X, or each X independently, is an electronwithdrawing group; and Y is a halogen atom; Z² is of the formula—SO₂CH₂CH₂X¹  (IV) wherein X¹ is an eliminatable group; or—SO₂(CH₂)_(z)CH═CH₂  (V) wherein Z is zero or 1; Ar is a benzene ornaphthalene nucleus; R³, or each R³ independently, is C₁₋₄ alkyl, nitro,halo or sulphonic acid or salt thereof; c is zero or 1-4; R⁴, or each R⁴independently, is a sulphonic acid or a salt thereof; and d is 1 or 2.12. A dye according to claim 9, wherein D is a disazo chromophore.
 13. Adye according to claim 12, which has the formula (XVIII)

wherein: one of Z⁵ and Z⁶ is a group Z¹ and the other is a group Z²;each of f and g independently is zero or 1; when Z⁵ or Z⁶ is a group ofthe formula (I), f or g respectively is 1 and when Z⁵ or Z⁶ is any ofthe groups of the formulae (IV) and (V), f or g respectively is zero;wherein: formula (I) is

wherein: n is 1 or 2; X, or each X independently, is an electronwithdrawing group; and Y is a halogen atom; wherein: formula (IV) is—SO₂CH₂CH₂X¹  (IV) wherein X¹ is an eliminatable group; and formula (V)is —SO₂(CH₂)_(z)CH═CH₂  (V) wherein z is zero or 1; each of c and e,independently, is zero or 1-4; d is 1 or 2; each R independently ishydrogen or optionally substituted C₁₋₄ alkyl, such that the same aminogroup presents itself to each of the reactive group Z¹ and the component(i) wherein component (i) is a chromophore D; each of Ar¹ and Ar² is anoptionally substituted aryl group; and each of R³ and R⁴ is C₁₋₄ alkyl,nitro, halo or sulphonic acid or salt thereof.
 14. A dye according toclaim 13, wherein one of Z⁵ and Z⁶ is a group

wherein: X is an electron withdrawing group, Y is a halogen atom and nis 1 or 2 and the other of Z⁵ and Z⁶ is the group —SO₂CH₂CH₂OSO₃H or—SO₂CH═CH₂.
 15. A dye according to claim 14, has the formula (XLIII)

wherein: G³ is C₂H₄OSO₃H or a salt thereof or —CH═CH₂; G¹ and G¹ aredifferent and are OH or NH₂; R⁴ is sulphonic acid or a salt thereof andd is 1 or 2; and each of h and i, independently, is zero, 1 or
 2. 16. Adye according to claim 15, wherein the dye has the formula (XLIV)

where each of G¹ and G² is different and is OH or NH₂ and G¹ isC₂H₄OSO₃H or a salt thereof or —CH═CH₂.
 17. A dye according to claim 1,of the formula (XXX) Z¹—L¹—D[L³]_(q)[Z³—L⁴]_(r)[J¹]_(s)Z²(XXX) wherein:Z³ is a third reactive group selected from the groups of the formulae(I)-(III), wherein: formula (I) is

in which: n is 1 or 2; X, or each X independently, is an electronwithdrawing group; and Y is a halogen atom; formula (II) is

wherein m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2,p is 0; Y¹, or each Y¹ independently, is a halogen atom or an optionallysubstituted pyridinium group; and T is C₁₋₄ alkoxy, C₁₋₄ thioalkoxy orN(R¹)(R²), wherein each of R¹ and R² independently is halogen,optionally substituted C₁₋₄ alkyl or optionally substituted aryl; andformula (III) is

wherein: x is 1, 2, or 3; y is zero, 1 or 2; and x+y≦3; Y², or each Y²independently, is a halogen atom or an optionally substituted pyridiniumgroup; and U or each U independently, is C₁₋₄ alkyl or C₁₋₄alkylsulphonyl; J¹ is an optionally substituted aryl group or achromophore; L³ is a linking group linking one of Z³ and J¹ to D; L⁴ isa linking group linking Z³ and J¹; each of q, r and s, independently, iszero or 1; and each of Z¹, Z² and L¹ is as defined in claim
 1. 18. A dyeaccording to claim 17, wherein each of L³ and L⁴, independently, isselected from one of the groups of the formulae (VII)¹, (VII)² and(VII)³,

wherein: R, or each R independently, is hydrogen or C₁₋₄ alkyl; B is ahydrocarbon bridging group which has at least two carbon atoms, isoptionally substituted, optionally includes at least one hetero atom andis optionally a chromophore; and b is from 2 to 6 inclusive.
 19. A dyeaccording to claim 18, wherein each of L³ and L⁴ is a group of theformulae (VII)¹, —N(R)—  (VII)¹ wherein R, or each R independently, ishydrogen or C₁₋₄ alkyl.
 20. A dye according to claim 7, wherein q is 1,r is zero and s is
 1. 21. A dye according to claim 20, wherein L³ is agroup of the formula (VII)³ —N(R)BN(R)—  (VII)³ wherein D is a triazinegroup substituted by a non-reactive group.
 22. A dye according to claim17, wherein the chromophore D is an azo chromophore derived from1-hydroxy-8-aminoaphthalene substituted by at least one sulphamic acidgroup.
 23. A dye according to claim 1 of the formula (XXXI)Z¹—L¹—D¹[L^(3—Z) ³(L⁴—Z⁴)₁L⁵—D²]_(k)Z²  (XXXI) wherein: D¹ is a firstchromophore; D² is a second chromophore; Z³, when present, is a thirdreactive group selected from the groups of the formulae (I)-(III), givenand defined in claim 17; Z⁴ when present, is a fourth reactive groupselected from the groups of the formulae (I)-(III), given and defined inclaim 17; L³ is a linking group linking Z³ to D¹; L⁴ is a linking grouplinking Z³ to Z⁴; L⁵ is a linking group linking D² to one of Z³ and Z⁴;each of k and l, independently, is zero or 1; and each of Z¹, Z² and L¹is as defined in claim
 1. 24. A dye according to claim 1, of the formula(XXXII) Z¹—L¹—Z³—L³—D—Z²  (XXXII) wherein: Z³ is a third reactive groupselected from the groups (I)-(III), given and defined in claim 17; andL³ is a third linking group selected from the groups (VII)¹, (VII)² and(VII)³,

wherein: R, or each R independently, is hydrogen or C₁₋₄ alkyl; B is ahydrocarbon bridging group which has at least two carbon atoms, isoptionally substituted, optionally includes at least one hetero atom andis optionally a chromophore; and b is from 2 to 6 inclusive; Z² is asecond reactive group selected from the groups (IV)-(V), given anddefined in claim 1; and each of Z¹ and L¹ is as defined in claim
 1. 25.A dye according to claim 24, wherein L¹ is a linking group of theformula (VII)² or (VII)³,

wherein: R, or each R independently, is hydrogen or C₁₋₄ alkyl; B is ahydrocarbon bridging group which has at least two carbon atoms, isoptionally substituted, optionally includes at least one hetero atom andis optionally a chromophore; and b is from 2 to 6 inclusive.
 26. A dyeaccording to claim 24, wherein Z³ is a group of the formula (II),

wherein m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2,p is 0, Y¹, or each Y¹ independently, is a halogen atom or an optionallysubstituted pyridinium group; and T is C₁₋₄alkoxy, C₁₋₄thioalkoxy orN(R¹)(R²), wherein each of R¹ and R² independently is halogen,optionally substituted C₁₋₄alkyl or optionally substituted aryl.
 27. Adye according to claim 24, wherein the chromophore D is a disazo dyecontaining a residue derived from H-acid and having azo groups at the 2-and 7- positions.
 28. A dye according to claim 1, wherein D is a groupof the formula (XLII)


29. A dye according to claim 1, of the formula (XXXVI)

wherein: one of Z³ and Z⁴ is a reactive group Z² selected from theformulae (IV) and (V), given and defined below; the other of Z³ and Z⁴,independently, is a reactive group selected from the formulae (IV)-(VI),given and defined below; each of t and u, independently, is zero or 1and at least one of t and a is 1; when Z³ is a reactive group Z², t is 1and when Z⁴ is a reactive group Z², a is 1; D is a chromophore; Ar is anoptionally substituted aryl group; L¹ is a group of the formula (XLI)

wherein each R, independently, is hydrogen or optionally substitutedC₁₋₄ alkyl; and Z¹ is a group of the formula (I), given and definedbelow; wherein: formula (I) is

wherein: n is 1 or 2; X, or each X independently, is an electronwithdrawing group; and Y is a halogen atom; formula (IV) is—SO₂CH₂CH₂X¹  (IV) wherein X¹ is an eliminatable group; formula (V) is—SO₂(CH₂)_(z)CH═CH₂  (V) wherein z is zero or 1; and formula (VI) is—W—C(R¹⁰)═CH₂  (VI) wherein: R¹⁰ is hydrogen, C₁₋₄ alkyl or halogen; andW is —OC(═O)— or —N(R¹¹)C(═O)— in which R¹¹ is hydrogen or C₁₋₄ alkyl.30. A dye according to claim 29, wherein D is a disazo dye containing aresidue derived from H-acid.
 31. A dye according to claim 1, of theformula (XXXVII) Z¹—L¹—D^(N)—Z²  (XXXVII) wherein: D^(N) is achromophore containing a heterocyclic group including a nitrogen atom;L¹ is a group of the formula (VII)⁴ or (VII)⁵,

wherein B is a hydrocarbon bridging group which has at least two carbonatoms, is optionally substituted, optionally includes at least onehetero group and is optionally a chromophore, R is hydrogen or C₁₋₄alkyl and b is from 2 to 6 inclusive; which group of the formula (VII)⁴or (VII)⁵ is directly attached via the bond {circle around (1)}, to thenitrogen atom of the said chromophore D^(N); and Z¹ is a halobenzene ofthe formula (I)

wherein: n is 1 or 2; X, or each X independently, is an electronwithdrawing group; and Y is a halogen atom; Z² is selected from thegroup consisting of (4) a group of the formula (IV) —SO₂CH₂CH₂X¹  (IV)wherein X¹ is an eliminatable group; and (5) a group of the formula (V)—SO₂(CH₂)_(z)CH═CH₂  (V) wherein z is zero or
 1. 32. A dye according toclaim 31, wherein the chromophore D has the formula (XLII)


33. A dye according to claim 10, which is an azo dye having at least twoazo groups therein.
 34. A dye according to my claim 9, wherein D is atrisazo or tetrakisazo chromophore.
 35. A dye of the formula


36. A dye of the formula


37. A process for preparing a dye of the formula (VIII)³Z¹—L¹—D—Z²  (VIII)³ wherein: D is a chromophore L¹ is N(R), in which Ris hydrogen or C₁₋₄ alkyl; Z¹ is a group

in which n is 1 or 2; X, or each X independently, is an electronwithdrawing group; and Y is a hydrogen atom; and Z² is a group of theformula (IV) —SO₂CH₂CH₂X¹  (IV) wherein X¹ is an eliminatable group; ora group of the formula (V) —SO₂(CH₂)₂CH═CH₂  (V) wherein z is zero or 1;which process comprises reacting a chromophoric compound of the formula(XXIV) H(R)N—D—Z²  (XXIV) wherein D and Z² are as defined above, with adihalobenzene compound of the formula (XXI)

wherein each of X, Y and n is as defined above, to obtain the dye of theformula (VIII)³.
 38. A process for the colouration of a substrate, whichprocess comprises applying to the substrate a dye according to claim 1.39. A process according to claim 38, wherein the dye is applied to thesubstrate by exhaust dyeing, padding or printing.
 40. A processaccording to claim 39, wherein the dye is applied by ink jet printing.